WO2012033161A1 - Cover glass for packaging semiconductor material, and process for production thereof - Google Patents

Cover glass for packaging semiconductor material, and process for production thereof Download PDF

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Publication number
WO2012033161A1
WO2012033161A1 PCT/JP2011/070480 JP2011070480W WO2012033161A1 WO 2012033161 A1 WO2012033161 A1 WO 2012033161A1 JP 2011070480 W JP2011070480 W JP 2011070480W WO 2012033161 A1 WO2012033161 A1 WO 2012033161A1
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Prior art keywords
glass
cover glass
semiconductor package
less
content
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PCT/JP2011/070480
Other languages
French (fr)
Japanese (ja)
Inventor
誉子 駒井
隆 村田
正弘 淀川
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日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to CN2011800437198A priority Critical patent/CN103097317A/en
Priority to US13/821,622 priority patent/US9269742B2/en
Publication of WO2012033161A1 publication Critical patent/WO2012033161A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/14618—Containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a cover glass for a semiconductor package that is attached to the front surface of a semiconductor package that houses a solid-state imaging device and a laser diode, and that protects the solid-state imaging device and the laser diode and is used as a transparent window.
  • the present invention relates to a cover glass of a plastic package in which a solid-state imaging device such as CMOS (Complementary Metal Oxide Semiconductor) is accommodated.
  • CMOS Complementary Metal Oxide Semiconductor
  • Optical semiconductors that are currently widely used as solid-state image sensors include CCDs (Charge Coupled Devices) and CMOS (Complementary Metal Oxide Semiconductors).
  • CCDs are mainly mounted on video cameras in order to capture high-definition images, but in recent years, the use range of images has been rapidly expanded as the use of image data processing has accelerated. In particular, they are mounted on digital still cameras and mobile phones, and are increasingly used to convert high-definition images into electronic information data.
  • CMOS also called complementary metal oxide semiconductor, can be downsized compared to a CCD, consumes less than 1/5 power, and can utilize the manufacturing process of a microprocessor.
  • a solid-state image sensor is placed in a semiconductor package made of a ceramic material such as alumina, a metal material, or a plastic material, and a flat cover glass serving as a transparent window is bonded with various organic resins or low-melting glass. Adhered with a material and hermetically sealed.
  • the semiconductor package cover glass is required to emit less ⁇ rays. This is because a soft error is caused when the amount of ⁇ rays emitted from the cover glass increases.
  • the ⁇ -ray emission from the glass is caused by the radioactive isotopes U (uranium) and Th (thorium) being contained as impurities in the glass. Therefore, when manufacturing glass, a high-purity raw material is used, or a refractory with a low radioactive isotope (eg, alumina electrocast refractory, quartz refractory, platinum) is used for the inner wall of the melting furnace for melting the raw material. Such measures are taken.
  • Patent Document 1 discloses a cover glass for a semiconductor package that has a thermal expansion coefficient compatible with that of a plastic package and that emits a small amount of ⁇ rays.
  • the cover glass used for them has strict standards for dirt, scratches, adhesion of foreign matter, etc. on its surface, and high-quality cleanliness. The degree is required. Further, in addition to the cleanliness of the surface, it is also required to prevent contamination of crystal defects inside the glass and foreign matters such as platinum. Further, this type of glass is required to have excellent weather resistance so as not to deteriorate the surface quality over a long period of time, to prevent breakage and deformation, and to have a low density so that the weight can be reduced.
  • the present invention has been made in view of such circumstances, and it is a technical problem to provide a cover glass for a semiconductor package that has characteristics suitable for a plastic package and that always emits a small amount of ⁇ -rays and a method for manufacturing the same.
  • the cover glass for a semiconductor package of the present invention is SiO 2 58 to 75%, Al 2 O 3 1.1 to 20%, B 2 O 3 0 to 10%, Na 2 O 0.1 to 20% by mass%. , K 2 O 0 to 11%, alkaline earth metal oxide 0 to 20%, an average coefficient of thermal expansion in the temperature range of 30 to 380 ° C. is 90 to 180 ⁇ 10 ⁇ 7 / ° C., and Young's modulus is 68 GPa or more. The amount of ⁇ rays emitted from the glass is 0.05 c / cm 2 ⁇ hr or less. “Average thermal expansion coefficient” means an average thermal expansion coefficient in a temperature range of 30 to 380 ° C.
  • the “ ⁇ -ray emission amount” is a value measured using an ultra-low level ⁇ -ray measuring apparatus (LACS-4000M manufactured by Sumitomo Chemical Co., Ltd.).
  • the thermal expansion coefficient and Young's modulus are compatible with the plastic package, even when used as a cover glass of the plastic package, warpage or deformation due to a difference in thermal expansion, or cracking or peeling of the glass does not occur. .
  • the U content in the glass is 100 ppb or less and the Th content is 200 ppb or less.
  • the ⁇ -ray emission amount can be accurately reduced.
  • ZrO 2 , As 2 O 3 and BaO are not substantially contained.
  • the ⁇ -ray emission amount can be accurately reduced.
  • the total amount of alkali metal oxide and alkaline earth metal oxide is preferably 21 to 35% by mass.
  • the “total amount of alkali metal oxide and alkaline earth metal oxide” means the total content of Na 2 O, K 2 O, Li 2 O, CaO, MgO, SrO, and BaO.
  • the glass viscosity at the liquidus temperature is preferably 10 4.7 dPa ⁇ s or more.
  • the liquidus temperature means a temperature measured as follows. First, each glass sample is crushed to a particle size of 300 to 500 ⁇ m, put into a platinum boat, and held in a temperature gradient furnace for 8 hours. Thereafter, the sample was observed with a microscope, and the highest temperature among the temperatures at which devitrification (crystal foreign matter) was observed inside the glass sample was defined as the liquidus temperature. The viscosity of the glass at the liquidus temperature was defined as the liquidus viscosity.
  • the conventional cover glass may not be able to accurately detect the presence or absence of foreign matter or dust during image inspection before shipment, or may cause malfunction.
  • the cause is considered as follows.
  • innumerable fine irregularities fine polishing flaws
  • the irradiated light is refracted due to the irregularities on the cover glass translucent surface, and there will be a mixture of parts that appear bright and parts that appear dark. It may cause the situation that the presence or absence of the cannot be detected accurately.
  • the cover glass for a semiconductor package preferably has an unpolished surface.
  • “Having an unpolished surface” means having a surface quality that can be used as a cover glass in an unpolished state. More specifically, it means that the surface roughness (Ra) is 1.0 nm or less.
  • the surface roughness (Ra) represents the quality of surface smoothness, and can be measured by applying a test method based on JIS B0601.
  • the precision polishing process can be omitted, it can be mass-produced at low cost.
  • the ratio of SiO 2 / (Al 2 O 3 + K 2 O) is preferably 1 to 12 on a mass basis.
  • the ratio of (Na 2 O + K 2 O) / Na 2 O is preferably 1.1 to 10 on a mass basis.
  • the cover glass for a semiconductor package of the present invention is preferably used for a plastic package for CMOS.
  • the manufacturing method of the semiconductor package of the present invention is, by mass%, SiO 2 58 to 75%, Al 2 O 3 1.1 to 20%, B 2 O 3 0 to 10%, Na 2 O 0.1 to 20%. , K 2 O 0 to 11%, alkaline earth metal oxide 0 to 20%, and glass raw material having an average coefficient of thermal expansion of 90 to 180 ⁇ 10 ⁇ 7 / ° C. in the temperature range of 30 to 380 ° C.
  • the glass raw material and the melting equipment are selected so that the amount of ⁇ -ray emitted from the glass is 0.05 c / cm 2 ⁇ hr or less while being formed into a plate shape using the overflow downdraw method after being prepared and melted It is characterized by performing.
  • “selection of melting equipment” means selecting and using a melting tank, a clarification tank or the like made of a material having a low content of radioisotope.
  • the cover glass of the present invention can be easily produced.
  • the raw material batch it is preferable to select the raw material batch and adjust the melting conditions so that the U content in the glass is 100 ppb or less and the Th content is 200 ppb or less.
  • the ⁇ -ray emission amount of the obtained glass can be accurately reduced.
  • the ⁇ -ray emission amount of the obtained glass can be accurately reduced.
  • the cover glass of the present invention is, by mass%, SiO 2 58 to 75%, Al 2 O 3 1.1 to 20%, B 2 O 3 0 to 10%, Na 2 O 0.1 to 20%, K 2. O 0.1 to 11%, alkaline earth metal oxide 0 to 20%.
  • SiO 2 is a main component serving as a skeleton constituting the glass, and has an effect of improving the weather resistance of the glass.
  • the content of SiO 2 is 58 to 75%, preferably 60 to 73%, more preferably 62 to 69%.
  • Al 2 O 3 is a component that increases the weather resistance and liquid phase viscosity of glass and improves the Young's modulus. However, if the content of Al 2 O 3 is too large, the high-temperature viscosity of the glass tends to increase and the meltability tends to deteriorate.
  • the content of Al 2 O 3 is 1.1 to 20%, preferably 1.1 to 18%, 1.1 to 17%, 1.1 to 17.5%, 3.5 to 16.5% More preferably, it is 4 to 16%.
  • B 2 O 3 is a component that works as a flux, lowers the viscosity of the glass, and improves the meltability. Furthermore, it is a component for increasing the liquid phase viscosity. However, if the content of B 2 O 3 is too large, the weather resistance of the glass tends to decrease.
  • the content of B 2 O 3 is 0 to 10%, preferably 0 to 9%, 0 to 8%, 0 to 5%, 0 to 3%, 0 to 2%, 0 to 1.9%, Preferably, it is 0 to 1%.
  • Alkali metal oxides (Na 2 O, K 2 O, Li 2 O) are components that lower the viscosity of the glass, improve the meltability, and effectively adjust the thermal expansion coefficient and liquid phase viscosity.
  • the total amount of alkali metal oxides is preferably 0 to 27%, preferably 1 to 27%, more preferably 5 to 25%, and particularly preferably 7 to 23%.
  • Na 2 O is particularly effective in adjusting the thermal expansion coefficient
  • K 2 O is effective in increasing the liquid phase viscosity. Therefore, when Na 2 O and K 2 O are used in combination, the thermal expansion coefficient and the liquid phase viscosity can be easily adjusted. Therefore it is preferable to contain as essential components Na 2 O and K 2 O in the present invention.
  • the content of Na 2 O is 0.1 to 20%, preferably 3 to 18%, more preferably 8 to 17%.
  • the content of K 2 O is 0 to 11%, preferably 0 to 9%, 0 to 7%, more preferably 0 to 2%, particularly preferably 0 to 1%.
  • the total amount of Na 2 O and K 2 O is preferably 4 to 22%, more preferably 6 to 20%.
  • Li 2 O can be contained. However, since Li 2 O tends to contain a radioisotope in the raw material, its content is preferably regulated to 0 to 5%, 0 to 3%, 0 to 1%, particularly 0 to 0.5%.
  • the ratio of (Na 2 O + K 2 O) / Na 2 O when regulated to be 1.1 to 10 on a mass basis, a high liquid phase viscosity is easily obtained.
  • the ratio of (Na 2 O + K 2 O) / Na 2 O is preferably 1.1 to 5, and more preferably 1.2 to 3.
  • Alkaline earth metal oxides are components that improve the weather resistance of the glass, lower the viscosity of the glass, and improve the meltability. However, if the content of these components is excessive, the glass tends to be devitrified and the density tends to increase.
  • the total content of the alkaline earth metal oxide is 0 to 20%, preferably 0.5 to 18%, more preferably 1.0 to 18%.
  • BaO and SrO tend to increase the density. Therefore, when it is desired to decrease the density, it is desirable to regulate each to 12% or less, particularly 10% or less. For the same reason, it is preferable to restrict the total amount of both to 6.5 to 13%.
  • BaO and SrO tend to contain radioactive isotopes in the raw material, when it is desired to reduce the amount of ⁇ -ray emission, it is preferably 0 to 3%, more preferably 0 to 1%, and still more preferably 0. It is desirably 0.8%, most preferably 0 to 0.5%, and if possible, it is desirably substantially not contained.
  • substantially free of BaO and SrO means that the contents of SrO and BaO in the glass composition are each 0.2% or less.
  • the average coefficient of thermal expansion in the temperature range of 30 to 380 ° C. is 90 to 180 ⁇ ⁇ 7 / ° C.
  • the total amount of alkali metal oxide and alkaline earth metal oxide is 21 to 35%, particularly 22 to 33%.
  • inconveniences such as a fall of a Young's modulus and a fall of a liquid phase viscosity, may arise.
  • 5% or less of components such as P 2 O 5 , Y 2 O 3 , Nb 2 O 3 , La 2 O 3 and the like are included within a range not impairing the properties of the glass. it can.
  • PbO, CdO, etc. are highly toxic and should be avoided.
  • various fining agents can be incorporated up to 3% in total.
  • the fining agent Sb 2 O 3 , Sb 2 O 5 , F 2 , Cl 2 , C, SO 3 , SnO 2 , or metal powder such as Al or Si can be used.
  • the SiO 2 —Al 2 O 3 —B 2 O 3 —RO system composition system containing SiO 2 , Al 2 O 3 , B 2 O 3 and alkaline earth metal oxides as essential components
  • the total amount of Sb 2 O 3 and Sb 2 O 5 is 0.05 to 2.0%
  • the total amount of F 2 , Cl 2 , SO 3 , C, and SnO 2 is 0.1 to 3.%. It is preferable to use the composition so that the ratio is 0% (particularly Cl 2 0.005 to 1.0%, SnO 2 0.01 to 1.0%).
  • SiO 2 —Al 2 O 3 —B 2 O 3 —R 2 O glass composition system containing SiO 2 , Al 2 O 3 , B 2 O 3 and alkali metal oxides as essential components
  • Sb 2 O 3 and Sb 2 O 5 are 0.2% or less in total
  • F 2 , Cl 2 , SO 3 , C, SnO 2 are 0.1 to 3.0 in total. It is preferable to make it contain so that it may become a ratio of%.
  • As 2 O 3 is capable of generating a clarification gas in a wide temperature range (about 1300 to 1700 ° C.), so far it has been widely used as a clarifier for this type of glass. Easy to contain elements. In addition, As 2 O 3 is very toxic and may contaminate the environment during the glass production process or waste glass processing. Therefore, As 2 O 3 should be substantially not contained. Further, Sb 2 O 3 and Sb 2 O 5 are components having an excellent clarification effect as well as As 2 O 3. However, since they are also highly toxic, it is desirable that they are not substantially contained if possible.
  • “substantially does not contain” means that the content of As 2 O 3 in the glass composition is 0.1% or less, desirably 100 ppm or less. Further, the contents of Sb 2 O 3 and Sb 2 O 5 are each 0.1% or less, desirably 0.09% or less, and most desirably 0.05%.
  • Fe 2 O 3 can also be used as a fining agent, but in order to color the glass, its content is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 200 ppm or less.
  • CeO 2 can also be used as a fining agent, but in order to color the glass, its content is preferably 2% or less, more preferably 1% or less, and even more preferably 0.7% or less.
  • ZrO 2 is a component that improves the strain point and Young's modulus of glass, but easily contains a radioisotope in the raw material. Therefore, the use of ZrO 2 has a high risk of causing an increase in the amount of ⁇ -ray emission.
  • ZrO 2 is a component that reduces devitrification resistance. In particular, when glass is formed by the overflow down-draw method, crystals due to ZrO 2 are deposited on the interface of the glass with the refractory, and there is a risk that productivity may be reduced during long-term operation.
  • the content of ZrO 2 is preferably 0 to 3%, 0 to 2%, 0 to 1%, 0 to 0.5%, particularly 0 to 0.2%, and if possible, it should not be substantially contained. desirable.
  • “substantially does not contain ZrO 2 ” means that the content of ZrO 2 in the glass composition is 500 ppm or less.
  • TiO 2 has the effect of improving the weather resistance of the glass and lowering the high-temperature viscosity.
  • TiO 2 promotes coloring by Fe 2 O 3 and is desirably not substantially contained.
  • substantially not containing TiO 2 means that the content of TiO 2 in the glass composition is 500 ppm or less. Note the TiO 2 if it can be less than 200ppm the content of Fe 2 O 3 may be contained up to 5%. However, enormous costs are required to make the Fe 2 O 3 content less than 200 ppm, which is not practical.
  • the cover glass for a semiconductor package of the present invention having the above composition can easily have an average coefficient of thermal expansion of 90 to 180 ⁇ 10 ⁇ 7 / ° C. in a temperature range of 30 to 380 ° C. Therefore, even if it is sealed with a plastic package (approximately 100 ⁇ 10 ⁇ 7 / ° C.) using an adhesive made of organic resin or low-melting glass, no internal distortion will occur and good sealing will be achieved over a long period of time. It is possible to keep the state.
  • a preferable thermal expansion coefficient of the cover glass is 90 to 160 ⁇ 10 ⁇ 7 / ° C., and a more preferable thermal expansion coefficient is 95 to 130 ⁇ 10 ⁇ 7 / ° C.
  • the cover glass for a semiconductor package of the present invention is preferably as the glass has a higher Young's modulus.
  • the Young's modulus of the glass is preferably 68 GPa or more, more preferably 70 GPa or more.
  • the Young's modulus represents how easily the cover glass is deformed in a state where a certain external force is applied. The larger the Young's modulus, the harder the cover glass is deformed.
  • the content of the alkali metal oxide is decreased, or the content of the alkaline earth metal oxide, Al 2 O 3 , B 2 O 3 or the like is increased. do it.
  • the cover glass for a semiconductor package of the present invention is preferably as the specific Young's modulus (Young's modulus / density) of the glass is higher. Specifically, it is desirable that the specific Young's modulus of the glass is 27 GPa / g ⁇ cm ⁇ 3 or more, particularly 28 GPa / g ⁇ cm ⁇ 3 or more.
  • a high specific Young's modulus satisfies the characteristics of being lightweight and difficult to deform, and is particularly suitable as a cover glass for semiconductor packages used in portable electronic devices.
  • the glass for semiconductor packages of the present invention is more preferable as the density of the glass is lower.
  • the density of glass is specifically 2.60 g / cm 3 or less, if it is particularly 2.55 g / cm 3 or less, is suitable for use to be mounted on a portable electronic device particularly used outdoors. That is, devices such as a video camera, a mobile phone, and a PDA (Personal Digital Assistant) are sometimes used outdoors, and thus are required to be lightweight and suitable for carrying.
  • the content of alkaline earth metal oxide or Al 2 O 3 may be decreased, or the content of B 2 O 3 may be increased.
  • the content of the alkali metal oxide may be reduced.
  • the cover glass for a semiconductor package of the present invention is preferably as the liquid phase viscosity is higher.
  • the viscosity of the glass in the formed portion is about 10 4.7 dPa ⁇ s.
  • the liquid phase viscosity of the glass is around 10 4.7 dPa ⁇ s or less, devitrified substances are likely to be generated in the molded glass.
  • devitrification occurs in the glass, the translucency is impaired, so that it cannot be used as a cover glass.
  • the liquid phase viscosity of the glass be as high as possible.
  • the liquid phase viscosity of the glass is 10 4.7 dPa ⁇ s or more, particularly 10 5.0 dPa ⁇ s. It is desirable that it is s or more. In the above range, in order to increase the liquid phase viscosity of the glass, the content of SiO 2 , alkaline earth metal oxide, etc. is decreased, or the content of alkali metal oxide, Al 2 O 3, etc. is increased. do it.
  • the cover glass for a semiconductor package of the present invention is characterized in that the amount of ⁇ rays emitted from the glass is 0.05 c / cm 2 ⁇ hr or less. If the amount of ⁇ -ray emission from the glass is small, even if it is mounted on a small solid-state imaging device with high pixels (for example, 1 million pixels or more), it is possible to reduce soft errors caused by ⁇ -rays. In order to reduce the amount of alpha rays emitted to 0.05 c / cm 2 ⁇ hr or less, mixing of impurities from raw materials and melting tanks is prevented, and the amount of U in the glass is suppressed to 100 ppb or less and the amount of Th is suppressed to 200 ppb or less.
  • the ⁇ ray emission amount of the window glass is 0.01 c / cm. 2 ⁇ hr or less, 0.0035 c / cm 2 or less, and particularly preferably 0.003 c / cm 2 or less.
  • the U amount is preferably 20 ppb or less, 5 ppb or less, particularly 4 ppb or less, and the Th amount is preferably 40 ppb or less, 10 ppb or less, and particularly preferably 8 ppb or less.
  • the allowable amount of U is smaller than the allowable amount of Th.
  • the light transmitting surface is more preferably a non-polished surface.
  • surface roughness (Ra) is preferably 1.0 nm or less, more preferably 0.5 nm or less, particularly preferably 0.3 nm. It is important to adopt a molding method capable of directly molding the following glass.
  • An overflow downdraw method is an example of such a method. In the overflow downdraw method, both the light-transmitting surfaces of the glass are molded without contact with other members, so that the glass surface becomes a free surface (fire-making surface), and the glass having excellent surface quality as described above is obtained. It can be obtained without polishing.
  • the thickness of the cover glass for a semiconductor package of the present invention is preferably 0.05 to 0.7 mm. As the wall thickness increases, it becomes an obstacle to weight reduction, and when it exceeds 0.7 mm, the distance from the solid-state imaging device becomes too close, and display defects may easily occur. On the other hand, if the thickness is less than 0.05 mm, the practical strength may be insufficient, or the deflection of the large plate glass may increase, making handling difficult.
  • a preferable thickness is 0.1 to 0.5 mm.
  • a glass raw material formulation is prepared so as to obtain a glass having a desired composition and characteristics.
  • the target glass composition and characteristics are as described above, and will not be described here.
  • a high-purity raw material with few impurities such as U and Th is used. More specifically, the high-purity raw material is selected so that the U content is 100 ppb or less (preferably 20 ppb or less) and the Th content is 200 ppb or less (preferably 40 ppb or less).
  • the prepared glass material is put into a melting tank and melted.
  • a platinum container may be used for the melting tank, it is better not to use it if possible because platinum particles are easily mixed in the glass.
  • at least the inner walls (ceiling, side surfaces, and bottom surface) of the melting tank are made of refractories with less U and Th.
  • alumina refractories for example, alumina-based electrocast bricks
  • quartz refractories for example, silica blocks
  • the homogenized molten glass is formed into a plate shape by the overflow down draw method to obtain a plate glass having a desired thickness.
  • the cover glass is produced by chopping the plate glass thus obtained into a predetermined size and chamfering as necessary.
  • the package cover glass thus obtained employs a high-purity raw material and a molten environment prepared so that impurities are hardly mixed while having the above basic composition. Therefore, desired characteristics can be obtained, and the contents of U, Th, Fe 2 O 3 , PbO, TiO 2 , ZrO 2 and the like can be precisely controlled.
  • cover glass for a package of the present invention will be described based on examples.
  • Tables 1 and 2 show examples (sample Nos. 1 to 11) of the cover glass for a package of the present invention.
  • a high-purity glass raw material prepared so as to have the composition shown in the table is put into a crucible made from any of platinum rhodium, alumina, and quartz, and the conditions of 1550 ° C. and 6 hours in an electric melting furnace having a stirring function
  • the molten glass was poured out onto a carbon plate. Furthermore, this plate glass was gradually cooled to obtain a glass sample, which was subjected to various evaluations.
  • each glass sample satisfied the conditions required for the cover glass for semiconductor packages in terms of density, thermal expansion coefficient, and ⁇ -ray emission amount. Moreover, since the temperature corresponding to the viscosity of 10 2.5 dPa ⁇ s is 1520 ° C. or lower, the meltability is excellent, the liquidus temperature is 1025 ° C. or lower, and the liquid phase viscosity is 10 5.0 dPa ⁇ s or higher. Therefore, it was confirmed that it was excellent in devitrification resistance and could be molded by the overflow down draw method.
  • the contents of U and Th were measured by ICP-MASS.
  • the density was measured by the well-known Archimedes method.
  • As the thermal expansion coefficient an average thermal expansion coefficient in a temperature range of 30 to 380 ° C. was measured using a dilatometer.
  • Young's modulus was measured by the resonance method. The specific Young's modulus was calculated from the Young's modulus and density measured by the bending resonance method.
  • the liquidus temperature is obtained by crushing each glass sample to a particle size of 300 to 500 ⁇ m, placing it in a platinum boat, holding it in a temperature gradient furnace for 8 hours, and then devitrifying (crystallizing) inside the glass sample by microscopic observation.
  • the maximum temperature at which foreign matter) was observed was measured, and that temperature was defined as the liquidus temperature.
  • the viscosity of the glass at the liquidus temperature was defined as the liquidus viscosity.
  • the strain point and annealing point were measured according to the method of ASTM C336-71, and the softening point was measured according to the method of ASTM C338-93.
  • the 10 4 dPa ⁇ s temperature, the 10 3 dPa ⁇ s temperature, and the 10 2.5 dPa ⁇ s temperature were determined by a well-known platinum ball pulling method.
  • the 10 2.5 dPa ⁇ s temperature is obtained by measuring a temperature corresponding to a high temperature viscosity of 10 2.5 dPa ⁇ s, and the lower this value, the better the meltability.
  • the amount of ⁇ -ray emission was measured using an ultra-low level ⁇ -ray measuring device (LACS-4000M manufactured by Sumitomo Chemical Co., Ltd.).
  • the acid resistance was defined as the weight per unit area of the sample changed before and after the test by immersing the glass sample in 10% hydrochloric acid at 80 ° C. for 24 hours.
  • the cover glass of each example has a surface roughness (Ra) of the first light-transmitting surface and the second light-transmitting surface of 0.23 nm or less, and has a very good smooth surface.
  • the cover glass for a package of the present invention is suitable as a cover glass for a solid-state imaging device package, and besides this, it can be used as a cover glass for various semiconductor packages including a package containing a laser diode. Further, since this cover glass has an average coefficient of thermal expansion of 90 to 180 ⁇ 10 ⁇ 7 / ° C. in the temperature range of 30 to 380 ° C., in addition to the plastic package, resin, Kovar alloy, molybdenum alloy, 42Ni—Fe The present invention can be applied to various packages made of an alloy, 45Ni—Fe alloy or the like.

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Abstract

Provided are: a cover glass for packaging a semiconductor material, which has a thermal expansion coefficient suitable for use in the packaging of a plastic material, on which the presence of a foreign matter, a dust or the like can be detected accurately in imaging testing, and from which α-ray is released in a reduced amount constantly; and a process for producing the cover glass. The cover glass is characterized by comprising, in mass%, 58-75% of SiO2, 1.1-20% of Al2O3, 0-10% of B2O3, 0.1-20% of Na2O, 0-11% of K2O and 0-20% of an alkali earth metal oxide and having an average thermal expansion coefficient of 90-180 × 10-7 /°C at a temperature ranging from 30 to 380˚C and a Young's modulus of 68 GPa or more, and is also characterized in that α-ray is released from the glass in an amount of 0.05 c/cm2·hr or less.

Description

半導体パッケージ用カバーガラス及びその製造方法Cover glass for semiconductor package and manufacturing method thereof
　本発明は、固体撮像素子やレーザーダイオードを収納する半導体パッケージの前面に取り付けられ、固体撮像素子やレーザーダイオードを保護すると共に透光窓として使用される半導体パッケージ用カバーガラスに関するものである。特にＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ　Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）等の固体撮像素子が収納されるプラスチックパッケージのカバーガラスに関するものである。 The present invention relates to a cover glass for a semiconductor package that is attached to the front surface of a semiconductor package that houses a solid-state imaging device and a laser diode, and that protects the solid-state imaging device and the laser diode and is used as a transparent window. In particular, the present invention relates to a cover glass of a plastic package in which a solid-state imaging device such as CMOS (Complementary Metal Oxide Semiconductor) is accommodated.
　固体撮像素子として、現在多く用いられている光半導体には、ＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）やＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ　Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）がある。ＣＣＤは、高精細な画像を取り込むため、主にビデオカメラに搭載されていたが、近年、画像のデータ処理の利用が加速する中で、急激に利用範囲が拡大している。特にデジタルスチルカメラや携帯電話に搭載され、高精細な画像を電子情報データに変換するために多く用いられるようになってきている。またＣＭＯＳは、相補型金属酸化物半導体とも呼ばれ、ＣＣＤに比較して小型化が可能であり、消費電力も５分の１程度と少なく、さらにマイクロプロセッサの製造工程を利用できるため、設備投資に費用が嵩まず、安価に製造することができる等の利点があり、携帯電話や小型パソコンといった画像入力デバイスに搭載されることが多くなってきている。 Optical semiconductors that are currently widely used as solid-state image sensors include CCDs (Charge Coupled Devices) and CMOS (Complementary Metal Oxide Semiconductors). CCDs are mainly mounted on video cameras in order to capture high-definition images, but in recent years, the use range of images has been rapidly expanded as the use of image data processing has accelerated. In particular, they are mounted on digital still cameras and mobile phones, and are increasingly used to convert high-definition images into electronic information data. CMOS, also called complementary metal oxide semiconductor, can be downsized compared to a CCD, consumes less than 1/5 power, and can utilize the manufacturing process of a microprocessor. However, it is advantageous in that it is inexpensive and can be manufactured at low cost, and it is increasingly installed in image input devices such as mobile phones and small personal computers.
　固体撮像素子は、アルミナ等のセラミック材料や金属材料、或いはプラスチック材料で形成された半導体パッケージ内に配置され、透光窓となる平板状のカバーガラスを各種の有機樹脂や低融点ガラスからなる接着材で接着して気密封止される。 A solid-state image sensor is placed in a semiconductor package made of a ceramic material such as alumina, a metal material, or a plastic material, and a flat cover glass serving as a transparent window is bonded with various organic resins or low-melting glass. Adhered with a material and hermetically sealed.
　半導体パッケージ用カバーガラスは、α線の放出が少ないことが求められる。カバーガラスからのα線の放出量が多くなると、ソフトエラーを引き起こすためである。ガラスからのα線放出は、放射性同位元素であるＵ（ウラン）やＴｈ（トリウム）が不純物としてガラスに含まれることが原因である。それゆえガラスの製造に際しては、高純度原料を採用したり、原料を溶解する溶融炉の内壁を放射性同位元素の少ない耐火物（例えばアルミナ電鋳耐火物、石英耐火物、白金）を用いたりする等の対策が採られている。 The semiconductor package cover glass is required to emit less α rays. This is because a soft error is caused when the amount of α rays emitted from the cover glass increases. The α-ray emission from the glass is caused by the radioactive isotopes U (uranium) and Th (thorium) being contained as impurities in the glass. Therefore, when manufacturing glass, a high-purity raw material is used, or a refractory with a low radioactive isotope (eg, alumina electrocast refractory, quartz refractory, platinum) is used for the inner wall of the melting furnace for melting the raw material. Such measures are taken.
　ところで近年、デジタルカメラやカメラ搭載携帯電話の普及に伴って高画素で小型軽量の撮像システムの需要が高まり、部材の省スペース化の要求も強まっている。このためパッケージ材料の小型化、薄型化が進んでいる。さらに部材全体を軽量化するために、プラスチック製のパッケージが注目されている。 In recent years, with the widespread use of digital cameras and camera-equipped mobile phones, the demand for high-pixel, small and lightweight imaging systems has increased, and there has been an increasing demand for space-saving components. For this reason, package materials are becoming smaller and thinner. Further, in order to reduce the weight of the entire member, a plastic package has attracted attention.
　このような事情から、プラスチックパッケージと熱膨張係数が適合し、且つα線放出量が少ない半導体パッケージ用カバーガラスが特許文献１に開示されている。 For these reasons, Patent Document 1 discloses a cover glass for a semiconductor package that has a thermal expansion coefficient compatible with that of a plastic package and that emits a small amount of α rays.
特開２００４－３２７９７８号公報JP 2004-327978 A
　ＣＣＤやＣＭＯＳは、画像を正確に電子情報に変換する必要性があるため、それに使用されるカバーガラスは、その表面に汚れや傷、異物の付着等に関して厳しい基準が設けられ、高品位の清浄度が要求されている。また表面の清浄度に加え、ガラス内部の結晶欠陥や白金等の異物の混入を防止することも要求されている。さらにこの種のガラスには、長期に亘って表面品位が低下しないよう耐候性に優れること、破損や変形が起こり難いこと、また軽量化できるように密度が低いことも要求される。 Since CCDs and CMOSs need to convert images to electronic information accurately, the cover glass used for them has strict standards for dirt, scratches, adhesion of foreign matter, etc. on its surface, and high-quality cleanliness. The degree is required. Further, in addition to the cleanliness of the surface, it is also required to prevent contamination of crystal defects inside the glass and foreign matters such as platinum. Further, this type of glass is required to have excellent weather resistance so as not to deteriorate the surface quality over a long period of time, to prevent breakage and deformation, and to have a low density so that the weight can be reduced.
　本発明は、このような事情に鑑みなされたものであり、プラスチックパッケージに適合する特性を有し、α線放出量が常に少ない半導体パッケージ用カバーガラスとその製造方法を提供することを技術的課題とする。 The present invention has been made in view of such circumstances, and it is a technical problem to provide a cover glass for a semiconductor package that has characteristics suitable for a plastic package and that always emits a small amount of α-rays and a method for manufacturing the same. And
　本発明の半導体パッケージ用カバーガラスは、質量％で、ＳｉＯ２　５８～７５％、Ａｌ２Ｏ３　１．１～２０％、Ｂ２Ｏ３　０～１０％、Ｎａ２Ｏ　０．１～２０％、Ｋ２Ｏ　０～１１％、アルカリ土類金属酸化物　０～２０％含有し、３０～３８０℃の温度範囲における平均熱膨張係数が９０～１８０×１０－７／℃、ヤング率が６８ＧＰａ以上、ガラスからのα線放出量が、０．０５ｃ／ｃｍ２・ｈｒ以下であることを特徴とする。
　「平均熱膨張係数」は、ディラトメーターを用いて測定した３０～３８０℃の温度範囲における平均熱膨張係数を意味する。「ヤング率」は共振法により測定した値を意味する。「α線放出量」は、超低レベルα線測定装置（住友化学社製ＬＡＣＳ－４０００Ｍ）を用いて測定した値である。 The cover glass for a semiconductor package of the present invention is SiO 2 58 to 75%, Al 2 O 3 1.1 to 20%, B 2 O 3 0 to 10%, Na 2 O 0.1 to 20% by mass%. , K 2 O 0 to 11%, alkaline earth metal oxide 0 to 20%, an average coefficient of thermal expansion in the temperature range of 30 to 380 ° C. is 90 to 180 × 10 −7 / ° C., and Young's modulus is 68 GPa or more. The amount of α rays emitted from the glass is 0.05 c / cm 2 · hr or less.
“Average thermal expansion coefficient” means an average thermal expansion coefficient in a temperature range of 30 to 380 ° C. measured using a dilatometer. “Young's modulus” means a value measured by a resonance method. The “α-ray emission amount” is a value measured using an ultra-low level α-ray measuring apparatus (LACS-4000M manufactured by Sumitomo Chemical Co., Ltd.).
　上記構成によれば、熱膨張係数およびヤング率がプラスチックパッケージに適合することから、プラスチックパッケージのカバーガラスとして使用しても、熱膨張差による反りや変形、あるいはガラスの割れや剥がれ等が生じない。 According to the above configuration, since the thermal expansion coefficient and Young's modulus are compatible with the plastic package, even when used as a cover glass of the plastic package, warpage or deformation due to a difference in thermal expansion, or cracking or peeling of the glass does not occur. .
　また特定組成を有することから、化学耐久性に優れ、密度の低いガラスを得ることができる。 Also, since it has a specific composition, it is possible to obtain a glass having excellent chemical durability and low density.
　本発明の半導体パッケージ用カバーガラスにおいては、ガラス中のＵ含有量が１００ｐｐｂ以下、Ｔｈ含有量が２００ｐｐｂ以下であることが好ましい。 In the cover glass for a semiconductor package of the present invention, it is preferable that the U content in the glass is 100 ppb or less and the Th content is 200 ppb or less.
　上記構成によれば、α線放出量を的確に低減することができる。 According to the above configuration, the α-ray emission amount can be accurately reduced.
　本発明においては、ＺｒＯ２、Ａｓ２Ｏ３及びＢａＯを実質的に含有しないことが好ましい。 In the present invention, it is preferable that ZrO 2 , As 2 O 3 and BaO are not substantially contained.
　上記構成によれば、α線放出量を的確に低減することができる。 According to the above configuration, the α-ray emission amount can be accurately reduced.
　本発明の半導体パッケージ用カバーガラスにおいては、アルカリ金属酸化物およびアルカリ土類金属酸化物の合量が２１～３５質量％であることが好ましい。「アルカリ金属酸化物及びアルカリ土類金属酸化物の合量」とは、Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ、ＣａＯ、ＭｇＯ、ＳｒＯ及びＢａＯの含有量の合量を意味する。 In the cover glass for a semiconductor package of the present invention, the total amount of alkali metal oxide and alkaline earth metal oxide is preferably 21 to 35% by mass. The “total amount of alkali metal oxide and alkaline earth metal oxide” means the total content of Na 2 O, K 2 O, Li 2 O, CaO, MgO, SrO, and BaO.
　上記構成によれば、ガラスの熱膨張係数を高めることが容易になる。 According to the above configuration, it becomes easy to increase the thermal expansion coefficient of the glass.
　本発明の半導体パッケージ用カバーガラスにおいては、液相温度におけるガラス粘度が１０４．７ｄＰａ・ｓ以上であることが好ましい。液相温度は次のようにして測定した温度を意味する。まず各ガラス試料を３００～５００μｍの粒径に破砕し、これを白金ボートに入れ、温度勾配炉中で８時間保持する。その後、試料を顕微鏡観察し、ガラス試料内部に失透（結晶異物）の見られた温度のうち、最高温度を液相温度とした。また液相温度におけるガラスの粘度を液相粘度とした。 In the cover glass for semiconductor packages of the present invention, the glass viscosity at the liquidus temperature is preferably 10 4.7 dPa · s or more. The liquidus temperature means a temperature measured as follows. First, each glass sample is crushed to a particle size of 300 to 500 μm, put into a platinum boat, and held in a temperature gradient furnace for 8 hours. Thereafter, the sample was observed with a microscope, and the highest temperature among the temperatures at which devitrification (crystal foreign matter) was observed inside the glass sample was defined as the liquidus temperature. The viscosity of the glass at the liquidus temperature was defined as the liquidus viscosity.
　上記構成によれば、オーバーフローダウンドロー法でガラスを成形することが容易になる。その結果、未研磨でも表面品位に優れたガラスを容易に得ることができる。 According to the above configuration, it becomes easy to form glass by the overflow downdraw method. As a result, it is possible to easily obtain a glass having excellent surface quality even when not polished.
　ところで従来のカバーガラスは、出荷前の画像検査で異物や塵等の有無を正確に検知できなかったり、誤作動を起こしたりするおそれがある。この原因は次のように考えられる。カバーガラスの透光面に精密研磨加工が施される結果、表面に無数の微細な凹凸（微小な研磨傷）が形成されることがある。微細な凹凸を有するカバーガラスを電子機器で画像検査すると、カバーガラス透光面の凹凸に起因して照射光が屈折し、明るく見える部分と暗く見える部分が混在することになり、異物や塵等の有無を正確に検知できないという事態を引き起こすことがある。 By the way, the conventional cover glass may not be able to accurately detect the presence or absence of foreign matter or dust during image inspection before shipment, or may cause malfunction. The cause is considered as follows. As a result of precision polishing being performed on the light-transmitting surface of the cover glass, innumerable fine irregularities (fine polishing flaws) may be formed on the surface. When a cover glass with fine irregularities is image-inspected with an electronic device, the irradiated light is refracted due to the irregularities on the cover glass translucent surface, and there will be a mixture of parts that appear bright and parts that appear dark. It may cause the situation that the presence or absence of the cannot be detected accurately.
　このような事態を防止したい場合、半導体パッケージ用カバーガラスは未研磨の表面を有することが好ましい。「未研磨の表面を有する」とは、未研磨の状態でカバーガラスとして使用可能な表面品位を有していることを意味する。より具体的には、表面粗さ（Ｒａ）が１．０ｎｍ以下であることを意味する。表面粗さ（Ｒａ）は、表面平滑性の品位を表すものであり、ＪＩＳ　Ｂ０６０１に基づく試験方法を適用することによって測定することができる。 In order to prevent such a situation, the cover glass for a semiconductor package preferably has an unpolished surface. “Having an unpolished surface” means having a surface quality that can be used as a cover glass in an unpolished state. More specifically, it means that the surface roughness (Ra) is 1.0 nm or less. The surface roughness (Ra) represents the quality of surface smoothness, and can be measured by applying a test method based on JIS B0601.
　上記構成によれば、未研磨の表面を有する、言い換えれば透光面に微細な凹凸や溝が存在しないことから、画像検査で異物や塵等の有無を正確に検知することができる。さらに入射光の散乱に起因する素子の誤動作を抑え、表示不良を防止することが可能である。しかも研磨しないため、酸化セリウムがガラス表面に残留することに起因するα線の放出を考慮する必要もない。 According to the above configuration, since there is an unpolished surface, in other words, there are no fine irregularities or grooves on the translucent surface, it is possible to accurately detect the presence or absence of foreign matter, dust or the like by image inspection. Further, malfunction of the element due to scattering of incident light can be suppressed, and display defects can be prevented. And since it does not grind | polish, it is not necessary to consider the discharge | release of the alpha ray resulting from cerium oxide remaining on the glass surface.
　また精密研磨加工工程を省略できるため、安価に大量生産することができる。 Moreover, since the precision polishing process can be omitted, it can be mass-produced at low cost.
　本発明の半導体パッケージ用カバーガラスにおいては、質量基準で、ＳｉＯ２／（Ａｌ２Ｏ３＋Ｋ２Ｏ）の比が１～１２であることが好ましい。 In the cover glass for a semiconductor package of the present invention, the ratio of SiO 2 / (Al 2 O 3 + K 2 O) is preferably 1 to 12 on a mass basis.
　上記構成によれば、ガラスの耐候性と溶融性を維持しながら、高い液相粘度を得ることが容易になる。 According to the above configuration, it is easy to obtain a high liquid phase viscosity while maintaining the weather resistance and meltability of the glass.
　本発明の半導体パッケージ用カバーガラスにおいては、質量基準で、（Ｎａ２Ｏ＋Ｋ２Ｏ）／Ｎａ２Ｏの比が１．１～１０であることが好ましい。 In the cover glass for a semiconductor package of the present invention, the ratio of (Na 2 O + K 2 O) / Na 2 O is preferably 1.1 to 10 on a mass basis.
　上記構成によれば、高い液相粘度を得ることが容易になる。 According to the above configuration, it is easy to obtain a high liquid phase viscosity.
　本発明の半導体パッケージ用カバーガラスにおいては、ＣＭＯＳ用プラスチックパッケージに使用されることが好ましい。 The cover glass for a semiconductor package of the present invention is preferably used for a plastic package for CMOS.
　本発明の半導体パッケージの製造方法は、質量％で、ＳｉＯ２　５８～７５％、Ａｌ２Ｏ３　１．１～２０％、Ｂ２Ｏ３　０～１０％、Ｎａ２Ｏ　０．１～２０％、Ｋ２Ｏ　０～１１％、アルカリ土類金属酸化物　０～２０％含有し、３０～３８０℃の温度範囲における平均熱膨張係数が９０～１８０×１０－７／℃となるようにガラス原料を調製し、溶融した後、オーバーフローダウンドロー法を用いて板状に成形するとともに、ガラスからのα線放出量が０．０５ｃ／ｃｍ２・ｈｒ以下となるようにガラス原料及び溶融設備の選択を行うことを特徴とする。本発明において「溶融設備の選択」とは、放射性同位元素の含有量が少ない材料で構成された溶融槽、清澄槽等を選択、使用することを意味する。 The manufacturing method of the semiconductor package of the present invention is, by mass%, SiO 2 58 to 75%, Al 2 O 3 1.1 to 20%, B 2 O 3 0 to 10%, Na 2 O 0.1 to 20%. , K 2 O 0 to 11%, alkaline earth metal oxide 0 to 20%, and glass raw material having an average coefficient of thermal expansion of 90 to 180 × 10 −7 / ° C. in the temperature range of 30 to 380 ° C. The glass raw material and the melting equipment are selected so that the amount of α-ray emitted from the glass is 0.05 c / cm 2 · hr or less while being formed into a plate shape using the overflow downdraw method after being prepared and melted It is characterized by performing. In the present invention, “selection of melting equipment” means selecting and using a melting tank, a clarification tank or the like made of a material having a low content of radioisotope.
　上記構成によれば、本発明のカバーガラスを容易に作製することができる。 According to the above configuration, the cover glass of the present invention can be easily produced.
　本発明の方法においては、ガラス中のＵ含有量が１００ｐｐｂ以下、Ｔｈ含有量が２００ｐｐｂ以下となるように、原料バッチの選択及び溶融条件の調節を行うことが好ましい。 In the method of the present invention, it is preferable to select the raw material batch and adjust the melting conditions so that the U content in the glass is 100 ppb or less and the Th content is 200 ppb or less.
　上記構成によれば、得られるガラスのα線放出量を的確に低減することができる。 According to the above configuration, the α-ray emission amount of the obtained glass can be accurately reduced.
　本発明の方法においては、ＺｒＯ２、Ａｓ２Ｏ３及びＢａＯを実質的に含有しないバッチを使用することが好ましい。 In the method of the present invention, it is preferable to use a batch substantially free of ZrO 2 , As 2 O 3 and BaO.
　上記構成によれば、得られるガラスのα線放出量を的確に低減することができる。 According to the above configuration, the α-ray emission amount of the obtained glass can be accurately reduced.
　本発明のカバーガラスは、質量％で、ＳｉＯ２　５８～７５％、Ａｌ２Ｏ３　１．１～２０％、Ｂ２Ｏ３　０～１０％、Ｎａ２Ｏ　０．１～２０％、Ｋ２Ｏ　０．１～１１％、アルカリ土類金属酸化物　０～２０％含有する。 The cover glass of the present invention is, by mass%, SiO 2 58 to 75%, Al 2 O 3 1.1 to 20%, B 2 O 3 0 to 10%, Na 2 O 0.1 to 20%, K 2. O 0.1 to 11%, alkaline earth metal oxide 0 to 20%.
　ガラス組成を上記のように限定した理由を以下に説明する。なお以下の説明では、特に説明のない限り「％」は「質量％」を意味する。 The reason for limiting the glass composition as described above will be described below. In the following description, “%” means “mass%” unless otherwise specified.
　ＳｉＯ２は、ガラスを構成する骨格となる主成分であり、ガラスの耐候性を向上する効果がある。ただしＳｉＯ２の含有量が多くなりすぎると、ガラスの高温粘度が上昇し、溶融性が悪化すると共に、液相粘度が高くなる傾向がある。ＳｉＯ２の含有量は５８～７５％であり、好ましくは６０～７３％、より好ましくは６２～６９％である。 SiO 2 is a main component serving as a skeleton constituting the glass, and has an effect of improving the weather resistance of the glass. However, when the content of SiO 2 is excessively increased, the high temperature viscosity of the glass is increased, the meltability is deteriorated, and the liquid phase viscosity tends to be increased. The content of SiO 2 is 58 to 75%, preferably 60 to 73%, more preferably 62 to 69%.
　Ａｌ２Ｏ３は、ガラスの耐候性と液相粘度を高め、ヤング率を向上させる成分である。ただしＡｌ２Ｏ３の含有量が多くなりすぎると、ガラスの高温粘度が上昇し、溶融性が悪化する傾向がある。Ａｌ２Ｏ３の含有量は１．１～２０％であり、好ましくは１．１～１８％、１．１～１７％、１．１～１７．５％、３．５～１６．５％、さらに好ましくは４～１６％である。 Al 2 O 3 is a component that increases the weather resistance and liquid phase viscosity of glass and improves the Young's modulus. However, if the content of Al 2 O 3 is too large, the high-temperature viscosity of the glass tends to increase and the meltability tends to deteriorate. The content of Al 2 O 3 is 1.1 to 20%, preferably 1.1 to 18%, 1.1 to 17%, 1.1 to 17.5%, 3.5 to 16.5% More preferably, it is 4 to 16%.
　Ｂ２Ｏ３は、融剤として働き、ガラスの粘性を下げ、溶融性を改善する成分である。さらに液相粘度を高めるための成分である。しかしＢ２Ｏ３の含有量が多くなりすぎると、ガラスの耐候性が低下する傾向がある。Ｂ２Ｏ３の含有量は０～１０％であり、好ましくは０～９％、０～８％、０～５％、０～３％、０～２％、０～１．９％、さらに好ましくは０～１％である。 B 2 O 3 is a component that works as a flux, lowers the viscosity of the glass, and improves the meltability. Furthermore, it is a component for increasing the liquid phase viscosity. However, if the content of B 2 O 3 is too large, the weather resistance of the glass tends to decrease. The content of B 2 O 3 is 0 to 10%, preferably 0 to 9%, 0 to 8%, 0 to 5%, 0 to 3%, 0 to 2%, 0 to 1.9%, Preferably, it is 0 to 1%.
　アルカリ金属酸化物（Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ）は、ガラスの粘性を下げ、溶融性を改善すると共に、熱膨張係数と液相粘度を効果的に調整する成分である。ただしアルカリ金属酸化物の含有量が多くなりすぎるとガラスの耐候性が著しく悪化する。よってアルカリ金属酸化物の含有量は、熱膨張係数と化学耐久性（アルカリ溶出量および耐候性）のバランス等を考慮して決める必要がある。アルカリ金属酸化物は合量で０～２７％であることが好ましく、１～２７％、さらには５～２５％、特に７～２３％であることが望ましい。 Alkali metal oxides (Na 2 O, K 2 O, Li 2 O) are components that lower the viscosity of the glass, improve the meltability, and effectively adjust the thermal expansion coefficient and liquid phase viscosity. However, if the content of the alkali metal oxide is too large, the weather resistance of the glass is significantly deteriorated. Therefore, it is necessary to determine the content of the alkali metal oxide in consideration of the balance between the thermal expansion coefficient and the chemical durability (the amount of alkali elution and weather resistance). The total amount of alkali metal oxides is preferably 0 to 27%, preferably 1 to 27%, more preferably 5 to 25%, and particularly preferably 7 to 23%.
　アルカリ金属酸化物の中で、特にＮａ２Ｏは熱膨張係数を調整する効果が大きく、またＫ２Ｏは液相粘度を上げる効果が大きい。そのためＮａ２ＯとＫ２Ｏを併用すると、熱膨張係数と液相粘度が調整しやすくなる。よって本発明ではＮａ２Ｏ及びＫ２Ｏを必須成分として含有することが好ましい。Ｎａ２Ｏの含有量は０．１～２０％であり、好ましくは３～１８％、さらに好ましくは８～１７％である。Ｋ２Ｏの含有量は０～１１％であり、好ましくは０～９％、０～７％、さらに好ましくは０～２％、特に好ましくは０～１％である。またＮａ２ＯとＫ２Ｏを合量で４～２２％が好ましく、６～２０％含有させることがより好ましい。なお本発明においてはＬｉ２Ｏを含有させることも可能である。ただしＬｉ２Ｏは、原料に放射性同位元素を含みやすいため、その含有量を０～５％、０～３％、０～１％、特に０～０．５％に規制することが好ましい。 Among the alkali metal oxides, Na 2 O is particularly effective in adjusting the thermal expansion coefficient, and K 2 O is effective in increasing the liquid phase viscosity. Therefore, when Na 2 O and K 2 O are used in combination, the thermal expansion coefficient and the liquid phase viscosity can be easily adjusted. Therefore it is preferable to contain as essential components Na 2 O and K 2 O in the present invention. The content of Na 2 O is 0.1 to 20%, preferably 3 to 18%, more preferably 8 to 17%. The content of K 2 O is 0 to 11%, preferably 0 to 9%, 0 to 7%, more preferably 0 to 2%, particularly preferably 0 to 1%. Further, the total amount of Na 2 O and K 2 O is preferably 4 to 22%, more preferably 6 to 20%. In the present invention, Li 2 O can be contained. However, since Li 2 O tends to contain a radioisotope in the raw material, its content is preferably regulated to 0 to 5%, 0 to 3%, 0 to 1%, particularly 0 to 0.5%.
　本発明において、（Ｎａ２Ｏ＋Ｋ２Ｏ）／Ｎａ２Ｏの比が質量基準で１．１～１０となるように規制すると、高い液相粘度が得られやすい。この（Ｎａ２Ｏ＋Ｋ２Ｏ）／Ｎａ２Ｏの比は、１．１～５であることが好ましく、１．２～３であることがより好ましい。 In the present invention, when the ratio of (Na 2 O + K 2 O) / Na 2 O is regulated to be 1.1 to 10 on a mass basis, a high liquid phase viscosity is easily obtained. The ratio of (Na 2 O + K 2 O) / Na 2 O is preferably 1.1 to 5, and more preferably 1.2 to 3.
　また本発明においては、ＳｉＯ２を低減し、Ａｌ２Ｏ３とＫ２Ｏを増加する程、液相粘度が上昇する傾向にある。そこでＳｉＯ２／（Ａｌ２Ｏ３＋Ｋ２Ｏ）の比を質量基準で１～１２、好ましくは２～１０となるように規制すると、ガラスの耐候性と溶融性を維持しながら、高い液相粘度を得ることが可能になる。 In the present invention, reducing SiO 2, as increasing Al 2 O 3 and K 2 O, there is a tendency that the liquid phase viscosity increases. Therefore, when the ratio of SiO 2 / (Al 2 O 3 + K 2 O) is controlled to be 1 to 12, preferably 2 to 10 on the mass basis, a high liquid phase is maintained while maintaining the weather resistance and meltability of the glass. It becomes possible to obtain a viscosity.
　アルカリ土類金属酸化物（ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ）は、ガラスの耐候性を向上させると共に、ガラスの粘性を下げ、溶融性を改善する成分である。ただしこれらの成分の含有量が多くなりすぎると、ガラスが失透しやすくなると共に密度が上昇する傾向がある。アルカリ土類金属酸化物の含有量は合量で０～２０％であり、好ましくは０．５～１８％、より好ましくは１．０～１８％である。 Alkaline earth metal oxides (MgO, CaO, SrO, BaO) are components that improve the weather resistance of the glass, lower the viscosity of the glass, and improve the meltability. However, if the content of these components is excessive, the glass tends to be devitrified and the density tends to increase. The total content of the alkaline earth metal oxide is 0 to 20%, preferably 0.5 to 18%, more preferably 1.0 to 18%.
　ただしアルカリ土類金属酸化物成分の中で、ＢａＯとＳｒＯは密度を上昇させやすいため、密度を低下したい場合は各々１２％以下、特に１０％以下に規制することが望ましい。同様の理由から、両者の合量を６．５～１３％に規制することが好ましい。またＢａＯとＳｒＯは、原料中に放射性同位元素を含みやすいため、α線放出量を低減したい場合は、各々０～３％とすることが好ましく、より好ましくは０～１％、さらに好ましくは０～０．８％、最も好ましくは０～０．５％であり、できれば実質的に含有しないことが望ましい。ここで「ＢａＯとＳｒＯを実質的に含有しない」とは、ガラス組成中のＳｒＯおよびＢａＯの含有量が各々０．２％以下であることを意味する。 However, among the alkaline earth metal oxide components, BaO and SrO tend to increase the density. Therefore, when it is desired to decrease the density, it is desirable to regulate each to 12% or less, particularly 10% or less. For the same reason, it is preferable to restrict the total amount of both to 6.5 to 13%. In addition, since BaO and SrO tend to contain radioactive isotopes in the raw material, when it is desired to reduce the amount of α-ray emission, it is preferably 0 to 3%, more preferably 0 to 1%, and still more preferably 0. It is desirably 0.8%, most preferably 0 to 0.5%, and if possible, it is desirably substantially not contained. Here, “substantially free of BaO and SrO” means that the contents of SrO and BaO in the glass composition are each 0.2% or less.
　本発明においては、３０～３８０℃の温度範囲における平均熱膨張係数が９０～１８０×-7／℃である。このような高熱膨張係数を達成するには、アルカリ金属酸化物およびアルカリ土類金属酸化物を多量に導入することが望ましい。具体的にはアルカリ金属酸化物およびアルカリ土類金属酸化物の合量が２１～３５％、特に２２～３３％であることが望ましい。なおこれらの成分の合量が多すぎる場合にはヤング率の低下、液相粘度の低下等の不都合が生じるおそれがある。 In the present invention, the average coefficient of thermal expansion in the temperature range of 30 to 380 ° C. is 90 to 180 × −7 / ° C. In order to achieve such a high thermal expansion coefficient, it is desirable to introduce a large amount of alkali metal oxide and alkaline earth metal oxide. Specifically, it is desirable that the total amount of alkali metal oxide and alkaline earth metal oxide is 21 to 35%, particularly 22 to 33%. In addition, when there is too much total amount of these components, there exists a possibility that inconveniences, such as a fall of a Young's modulus and a fall of a liquid phase viscosity, may arise.
　本発明においては、上記成分以外にも、ガラスの特性を損なわない範囲で、Ｐ２Ｏ５、Ｙ２Ｏ３、Ｎｂ２Ｏ３、Ｌａ２Ｏ３等の成分を５％以下含有させることができる。ただしＰｂＯ、ＣｄＯ等は毒性が強いため、使用を避けるべきである。 In the present invention, in addition to the above components, 5% or less of components such as P 2 O 5 , Y 2 O 3 , Nb 2 O 3 , La 2 O 3 and the like are included within a range not impairing the properties of the glass. it can. However, PbO, CdO, etc. are highly toxic and should be avoided.
　本発明においては、各種清澄剤を合量で３％まで含有させることができる。清澄剤としては、Ｓｂ２Ｏ３、Ｓｂ２Ｏ５、Ｆ２、Ｃｌ２、Ｃ、ＳＯ３、ＳｎＯ２、或いはＡｌ、Ｓｉ等の金属粉末が使用できる。 In the present invention, various fining agents can be incorporated up to 3% in total. As the fining agent, Sb 2 O 3 , Sb 2 O 5 , F 2 , Cl 2 , C, SO 3 , SnO 2 , or metal powder such as Al or Si can be used.
　本発明におけるＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３－ＲＯ系（ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３及びアルカリ土類金属酸化物を必須成分とする組成系）ガラスの場合は、清澄剤として、Ｓｂ２Ｏ３とＳｂ２Ｏ５が合量で０．０５～２．０％、Ｆ２、Ｃｌ２、ＳＯ３、Ｃ、ＳｎＯ２が合量で０．１～３．０％（特にＣｌ２　０．００５～１．０％、ＳｎＯ２　０．０１～１．０％）の割合となるように使用するのが好適である。またＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３－Ｒ２Ｏ系（ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３及びアルカリ金属酸化物を必須成分とする組成系）ガラスの場合は、溶融性に優れているため、Ｓｂ２Ｏ３とＳｂ２Ｏ５が合量で０．２％以下、Ｆ２、Ｃｌ２、ＳＯ３、Ｃ、ＳｎＯ２が合量で０．１～３．０％の割合となるように含有させることが好ましい。 In the case of the SiO 2 —Al 2 O 3 —B 2 O 3 —RO system (composition system containing SiO 2 , Al 2 O 3 , B 2 O 3 and alkaline earth metal oxides as essential components) glass in the present invention, As a clarifier, the total amount of Sb 2 O 3 and Sb 2 O 5 is 0.05 to 2.0%, and the total amount of F 2 , Cl 2 , SO 3 , C, and SnO 2 is 0.1 to 3.%. It is preferable to use the composition so that the ratio is 0% (particularly Cl 2 0.005 to 1.0%, SnO 2 0.01 to 1.0%). In the case of SiO 2 —Al 2 O 3 —B 2 O 3 —R 2 O glass (composition system containing SiO 2 , Al 2 O 3 , B 2 O 3 and alkali metal oxides as essential components) glass, Sb 2 O 3 and Sb 2 O 5 are 0.2% or less in total, and F 2 , Cl 2 , SO 3 , C, SnO 2 are 0.1 to 3.0 in total. It is preferable to make it contain so that it may become a ratio of%.
　なおＡｓ２Ｏ３は、幅広い温度域（１３００～１７００℃程度）で清澄ガスを発生させることができるため、従来、この種のガラスの清澄剤として広く用いられているが、原料中に放射性同位元素を含みやすい。しかもＡｓ２Ｏ３は、毒性が非常に強く、ガラスの製造工程や廃ガラスの処理時等に環境を汚染する可能性がある。よってＡｓ２Ｏ３は実質的に含有しないようにすべきである。さらに、Ｓｂ２Ｏ３、Ｓｂ２Ｏ５も、Ａｓ２Ｏ３と同様、清澄効果に優れた成分であるが、やはり毒性が強いため、できれば実質的に含有しないことが望ましい。ここで「実質的に含有しない」とは、ガラス組成中の、Ａｓ２Ｏ３の含有量が０．１％以下、望ましくは１００ｐｐｍ以下であることを意味する。またＳｂ２Ｏ３、Ｓｂ２Ｏ５の含有量は各々０．１％以下、望ましくは０．０９％以下、最も望ましくは０．０５％であることを意味する。 As 2 O 3 is capable of generating a clarification gas in a wide temperature range (about 1300 to 1700 ° C.), so far it has been widely used as a clarifier for this type of glass. Easy to contain elements. In addition, As 2 O 3 is very toxic and may contaminate the environment during the glass production process or waste glass processing. Therefore, As 2 O 3 should be substantially not contained. Further, Sb 2 O 3 and Sb 2 O 5 are components having an excellent clarification effect as well as As 2 O 3. However, since they are also highly toxic, it is desirable that they are not substantially contained if possible. Here, “substantially does not contain” means that the content of As 2 O 3 in the glass composition is 0.1% or less, desirably 100 ppm or less. Further, the contents of Sb 2 O 3 and Sb 2 O 5 are each 0.1% or less, desirably 0.09% or less, and most desirably 0.05%.
　またＦｅ２Ｏ３も清澄剤として使用できるが、ガラスを着色するため、その含有量は好ましくは５００ｐｐｍ以下、より好ましくは３００ｐｐｍ以下、さらに好ましくは２００ｐｐｍ以下に規制する。ＣｅＯ２も清澄剤として使用できるが、ガラスを着色するため、その含有量は好ましくは２％以下、より好ましくは１％以下、さらに好ましくは０．７％以下に規制する。 Fe 2 O 3 can also be used as a fining agent, but in order to color the glass, its content is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 200 ppm or less. CeO 2 can also be used as a fining agent, but in order to color the glass, its content is preferably 2% or less, more preferably 1% or less, and even more preferably 0.7% or less.
　ＺｒＯ２は、ガラスの歪点やヤング率を向上させる成分であるが、原料中に放射性同位元素を含みやすい。よってＺｒＯ２の使用はα線放出量の増大を招く危険性が高い。またＺｒＯ２は、耐失透性を低下させる成分である。特にオーバーフローダウンドロー法によってガラスを成形する場合、ガラスの耐火物と接触する界面にＺｒＯ２に起因する結晶が析出し、長期間に亘る操業中に生産性を低下させる虞がある。よってＺｒＯ２の含有量は０～３％、０～２％、０～１％、０～０．５％、特に０～０．２％にすることが好ましく、できれば実質的に含有しないことが望ましい。ここで「ＺｒＯ２を実質的に含有しない」とは、ガラス組成中のＺｒＯ２の含有量が５００ｐｐｍ以下であることを意味する。 ZrO 2 is a component that improves the strain point and Young's modulus of glass, but easily contains a radioisotope in the raw material. Therefore, the use of ZrO 2 has a high risk of causing an increase in the amount of α-ray emission. ZrO 2 is a component that reduces devitrification resistance. In particular, when glass is formed by the overflow down-draw method, crystals due to ZrO 2 are deposited on the interface of the glass with the refractory, and there is a risk that productivity may be reduced during long-term operation. Therefore, the content of ZrO 2 is preferably 0 to 3%, 0 to 2%, 0 to 1%, 0 to 0.5%, particularly 0 to 0.2%, and if possible, it should not be substantially contained. desirable. Here, “substantially does not contain ZrO 2 ” means that the content of ZrO 2 in the glass composition is 500 ppm or less.
　ＴｉＯ２は、ガラスの耐候性を改善し、高温粘度を低下させる効果を有するが、Ｆｅ２Ｏ３と共存させると、Ｆｅ２Ｏ３による着色を助長するため実質的に含有しないことが望ましい。ここで「ＴｉＯ２を実質的に含有しない」とは、ガラス組成中のＴｉＯ２の含有量が５００ｐｐｍ以下であることを意味する。なおＦｅ２Ｏ３の含有量を２００ｐｐｍ未満にすることができればＴｉＯ２を５％まで含有させることができる。しかしＦｅ２Ｏ３の含有量を２００ｐｐｍ未満にするには多大なコストがかかり、現実的でない。 TiO 2 has the effect of improving the weather resistance of the glass and lowering the high-temperature viscosity. However, when coexisting with Fe 2 O 3 , TiO 2 promotes coloring by Fe 2 O 3 and is desirably not substantially contained. Here, “substantially not containing TiO 2 ” means that the content of TiO 2 in the glass composition is 500 ppm or less. Note the TiO 2 if it can be less than 200ppm the content of Fe 2 O 3 may be contained up to 5%. However, enormous costs are required to make the Fe 2 O 3 content less than 200 ppm, which is not practical.
　以上の組成を有する本発明の半導体パッケージ用カバーガラスは、３０～３８０℃の温度範囲における平均熱膨張係数を９０～１８０×１０－７／℃にすることが容易である。よって有機樹脂や低融点ガラスからなる接着材を用いてプラスチックパッケージ（約１００×１０－７／℃）と封着しても、内部に歪みが発生せず、長期間に亘って良好な封着状態を保つことが可能である。カバーガラスの好ましい熱膨張係数は、９０～１６０×１０－７／℃、より好ましい熱膨張係数は９５～１３０×１０－７／℃である。 The cover glass for a semiconductor package of the present invention having the above composition can easily have an average coefficient of thermal expansion of 90 to 180 × 10 −7 / ° C. in a temperature range of 30 to 380 ° C. Therefore, even if it is sealed with a plastic package (approximately 100 × 10 −7 / ° C.) using an adhesive made of organic resin or low-melting glass, no internal distortion will occur and good sealing will be achieved over a long period of time. It is possible to keep the state. A preferable thermal expansion coefficient of the cover glass is 90 to 160 × 10 −7 / ° C., and a more preferable thermal expansion coefficient is 95 to 130 × 10 −7 / ° C.
　上記組成範囲であれば、低密度、高耐候性、高液相粘度のガラスを得ることが容易である。 In the above composition range, it is easy to obtain a glass with low density, high weather resistance, and high liquid phase viscosity.
　本発明の半導体パッケージ用カバーガラスは、ガラスのヤング率が高いほど好ましい。具体的にはガラスのヤング率が６８ＧＰａ以上、さらには７０ＧＰａ以上であることが好ましい。ヤング率はカバーガラスが一定の外力を加えられた状態でどれだけ変形しやすくなるかを表しており、ヤング率が大きいほどカバーガラスは変形し難くなる。カバーガラスのヤング率が高いほど、半導体素子に直接圧力が加わるのを防止し、結果として素子の損傷が防止できる。上記範囲において、ガラスのヤング率を高くするには、アルカリ金属酸化物の含有量を低下させたり、アルカリ土類金属酸化物、Ａｌ２Ｏ３、Ｂ２Ｏ３等の含有量を増加させたりすればよい。 The cover glass for a semiconductor package of the present invention is preferably as the glass has a higher Young's modulus. Specifically, the Young's modulus of the glass is preferably 68 GPa or more, more preferably 70 GPa or more. The Young's modulus represents how easily the cover glass is deformed in a state where a certain external force is applied. The larger the Young's modulus, the harder the cover glass is deformed. As the Young's modulus of the cover glass is higher, it is possible to prevent pressure from being directly applied to the semiconductor element, and as a result, damage to the element can be prevented. In the above range, in order to increase the Young's modulus of the glass, the content of the alkali metal oxide is decreased, or the content of the alkaline earth metal oxide, Al 2 O 3 , B 2 O 3 or the like is increased. do it.
　本発明の半導体パッケージ用カバーガラスは、ガラスの比ヤング率（ヤング率／密度）が高いほど好ましい。具体的にはガラスの比ヤング率が２７ＧＰａ／ｇ・ｃｍ－３以上、特に２８ＧＰａ／ｇ・ｃｍ－３以上であることが望ましい。比ヤング率が高ければ、軽量でかつ変形し難いという特性を満足するものとなるため、特に携帯用電子機器に使用される半導体パッケージ用カバーガラスとして好適である。 The cover glass for a semiconductor package of the present invention is preferably as the specific Young's modulus (Young's modulus / density) of the glass is higher. Specifically, it is desirable that the specific Young's modulus of the glass is 27 GPa / g · cm −3 or more, particularly 28 GPa / g · cm −3 or more. A high specific Young's modulus satisfies the characteristics of being lightweight and difficult to deform, and is particularly suitable as a cover glass for semiconductor packages used in portable electronic devices.
　本発明の半導体パッケージ用ガラスは、ガラスの密度が低いほど好ましい。具体的にはガラスの密度は２．６０ｇ／ｃｍ３以下、特に２．５５ｇ／ｃｍ３以下であると、特に屋外で使用する携帯用電子機器に搭載される用途に好適である。すなわちビデオカメラ、携帯電話、ＰＤＡ（Ｐｅｒｓｏｎａｌ　Ｄｉｇｉｔａｌ　Ａｓｓｉａｔａｎｔ）等の機器は、屋外で使用されることがあるため、軽量で持ち運びに適することが要求される。上記範囲において、ガラスの密度を低下させるには、例えばアルカリ土類金属酸化物やＡｌ２Ｏ３の含有量を低下させたり、Ｂ２Ｏ３の含有量を増加させたりすればよい。 The glass for semiconductor packages of the present invention is more preferable as the density of the glass is lower. The density of glass is specifically 2.60 g / cm 3 or less, if it is particularly 2.55 g / cm 3 or less, is suitable for use to be mounted on a portable electronic device particularly used outdoors. That is, devices such as a video camera, a mobile phone, and a PDA (Personal Digital Assistant) are sometimes used outdoors, and thus are required to be lightweight and suitable for carrying. In the above range, in order to decrease the density of the glass, for example, the content of alkaline earth metal oxide or Al 2 O 3 may be decreased, or the content of B 2 O 3 may be increased.
　また屋外で使用する携帯用電子機器に搭載される場合、軽量で持ち運びに適することに加え、高い耐候性を有することが要求される。つまり屋外で過酷な環境下で使用されても表面品位が低下しないといった特性を併せ持つことが望まれる。上記範囲において、ガラスの耐候性を向上させるには、例えばアルカリ金属酸化物の含有量を低下させればよい。 Also, when mounted on a portable electronic device used outdoors, it is required to have high weather resistance in addition to being lightweight and suitable for carrying. In other words, it is desirable to have such characteristics that the surface quality does not deteriorate even when used outdoors in harsh environments. In the above range, in order to improve the weather resistance of the glass, for example, the content of the alkali metal oxide may be reduced.
　本発明の半導体パッケージ用カバーガラスは、液相粘度が高いほど好ましい。つまりＳｉＯ２－Ａｌ２Ｏ３－Ｂ２Ｏ３－ＲＯ（又はＲ２Ｏ）系ガラスをオーバーフローダウンドロー法で成形する場合、成形部分におけるガラスの粘度はおよそ１０４．７ｄＰａ・ｓ程度となる。そのためガラスの液相粘度が１０４．７ｄＰａ・ｓ付近、或いはそれ以下であると、成形されたガラスに失透物が発生しやすい。ガラス中に失透物が発生すると、透光性が損なわれるため、カバーガラスとしては使用できなくなる。よってオーバーフローダウンドロー法でガラスを成形する場合、ガラスの液相粘度ができるだけ高いことが好ましく、具体的にはガラスの液相粘度が１０４．７ｄＰａ・ｓ以上、特に１０５．０ｄＰａ・ｓ以上であることが望ましい。上記範囲において、ガラスの液相粘度を高くするには、ＳｉＯ２、アルカリ土類金属酸化物等の含有量を低下させたり、アルカリ金属酸化物、Ａｌ２Ｏ３等の含有量を増加させたりすればよい。 The cover glass for a semiconductor package of the present invention is preferably as the liquid phase viscosity is higher. In other words, when the SiO 2 —Al 2 O 3 —B 2 O 3 —RO (or R 2 O) glass is formed by the overflow downdraw method, the viscosity of the glass in the formed portion is about 10 4.7 dPa · s. Become. For this reason, when the liquid phase viscosity of the glass is around 10 4.7 dPa · s or less, devitrified substances are likely to be generated in the molded glass. When devitrification occurs in the glass, the translucency is impaired, so that it cannot be used as a cover glass. Therefore, when glass is formed by the overflow down draw method, it is preferable that the liquid phase viscosity of the glass be as high as possible. Specifically, the liquid phase viscosity of the glass is 10 4.7 dPa · s or more, particularly 10 5.0 dPa · s. It is desirable that it is s or more. In the above range, in order to increase the liquid phase viscosity of the glass, the content of SiO 2 , alkaline earth metal oxide, etc. is decreased, or the content of alkali metal oxide, Al 2 O 3, etc. is increased. do it.
　また本発明の半導体パッケージ用カバーガラスは、ガラスからのα線放出量が０．０５ｃ／ｃｍ２・ｈｒ以下であることを特徴とする。ガラスからのα線放出量が少なければ、高画素（例えば１００万画素以上）で小型の固体撮像装置に搭載しても、α線に起因するソフトエラーの低減を図ることができる。α線放出量を０．０５ｃ／ｃｍ２・ｈｒ以下にするためには、原料や溶融槽からの不純物の混入を防止し、ガラス中のＵ量を１００ｐｐｂ以下、Ｔｈ量を２００ｐｐｂ以下に抑えることが望ましい。近年、固体撮像素子は、ますます画素数が大きくなっており、それに伴ってα線に起因するソフトエラーが発生しやすくなっているため、窓ガラスのα線放出量は、０．０１ｃ／ｃｍ２・ｈｒ以下、０．００３５ｃ／ｃｍ２以下、特に０．００３ｃ／ｃｍ２以下にすることが好ましい。またＵ量は２０ｐｐｂ以下、５ｐｐｂ以下、特に４ｐｐｂ以下にすることが好ましく、Ｔｈ量は４０ｐｐｂ以下、１０ｐｐｂ以下、特に８ｐｐｂ以下にすることが好ましい。尚、Ｕは、Ｔｈに比べて、α線を放出しやすいため、Ｕの許容量は、Ｔｈの許容量に比べて少なくなる。なおα線放出量を少なくする、或いはＵ、Ｔｈ量を低減するには、放射性元素を不純物として多量に含むＺｒＯ２、ＢａＯ等のガラス原料を極力使用しないようにすること、高純度原料を選択すること、溶融炉の内壁を放射性同位元素の少ない耐火物で構成すること、研磨工程を必要としない方法でガラスを成形すること（＝オーバーフローダウンドロー法を採用すること）等が挙げられる。 In addition, the cover glass for a semiconductor package of the present invention is characterized in that the amount of α rays emitted from the glass is 0.05 c / cm 2 · hr or less. If the amount of α-ray emission from the glass is small, even if it is mounted on a small solid-state imaging device with high pixels (for example, 1 million pixels or more), it is possible to reduce soft errors caused by α-rays. In order to reduce the amount of alpha rays emitted to 0.05 c / cm 2 · hr or less, mixing of impurities from raw materials and melting tanks is prevented, and the amount of U in the glass is suppressed to 100 ppb or less and the amount of Th is suppressed to 200 ppb or less. Is desirable. In recent years, the solid-state imaging device has an increasing number of pixels, and accordingly, soft errors due to α rays are likely to occur. Therefore, the α ray emission amount of the window glass is 0.01 c / cm. 2 · hr or less, 0.0035 c / cm 2 or less, and particularly preferably 0.003 c / cm 2 or less. The U amount is preferably 20 ppb or less, 5 ppb or less, particularly 4 ppb or less, and the Th amount is preferably 40 ppb or less, 10 ppb or less, and particularly preferably 8 ppb or less. In addition, since U emits alpha rays more easily than Th, the allowable amount of U is smaller than the allowable amount of Th. In order to reduce the amount of α-ray emission or reduce the amount of U and Th, use glass materials such as ZrO 2 and BaO containing a large amount of radioactive elements as impurities as much as possible, and select high-purity materials. And forming the inner wall of the melting furnace with a refractory material with less radioisotope, forming glass by a method that does not require a polishing step (= adopting an overflow downdraw method), and the like.
　本発明の半導体パッケージ用カバーガラスは、透光面が無研磨面であるとより好ましい。なお研磨することなく使用するためには、表面品位の高いガラス、具体的には表面粗さ（Ｒａ）が好ましくは１．０ｎｍ以下、さらには好ましくは０．５ｎｍ以下、特に好ましくは０．３ｎｍ以下のガラスを直接成形することが可能な成形法を採用することが重要である。このような方法としてオーバーフローダウンドロー法が挙げられる。オーバーフローダウンドロー法は、ガラスの両透光面が他の部材と接触することなく成形されることから、ガラス表面が自由表面（火造り面）となり、上記したような表面品位に優れたガラスを研磨することなしに得ることができる。カバーガラスの透光面の表面粗さ（Ｒａ）が小さくなるほど、異物等を検知する画像検査の精度が増し、また散乱光に起因する素子の誤動作の発生率が低下する。また半導体パッケージやデバイスの設計には厳密な寸法精度が求められる。半導体パッケージ用カバーガラスの肉厚偏差が大きく板厚が変化すると、これらの設計に大きな影響を与えてしまう。また厚肉のカバーガラスを作製し、後工程で研磨量を多くすると、基板作製に大きなコストがかかる。オーバーフローダウンドロー法では、板厚の偏差が少ない基板を低コストで作製することができる。 In the cover glass for a semiconductor package of the present invention, the light transmitting surface is more preferably a non-polished surface. In order to use without polishing, glass with high surface quality, specifically, surface roughness (Ra) is preferably 1.0 nm or less, more preferably 0.5 nm or less, particularly preferably 0.3 nm. It is important to adopt a molding method capable of directly molding the following glass. An overflow downdraw method is an example of such a method. In the overflow downdraw method, both the light-transmitting surfaces of the glass are molded without contact with other members, so that the glass surface becomes a free surface (fire-making surface), and the glass having excellent surface quality as described above is obtained. It can be obtained without polishing. As the surface roughness (Ra) of the light-transmitting surface of the cover glass decreases, the accuracy of image inspection for detecting foreign matter and the like increases, and the incidence of malfunction of elements due to scattered light decreases. In addition, strict dimensional accuracy is required for designing semiconductor packages and devices. When the thickness deviation of the cover glass for semiconductor packages is large and the plate thickness changes, these designs are greatly affected. Further, if a thick cover glass is produced and the amount of polishing is increased in a subsequent process, a large cost is required for producing the substrate. In the overflow downdraw method, a substrate with a small deviation in plate thickness can be manufactured at low cost.
　本発明の半導体パッケージ用カバーガラスは、肉厚が０．０５～０．７ｍｍであることが好ましい。肉厚が大きくなるほど、軽量化の障害となり、また０．７ｍｍ超では、固体撮像素子との距離が近くなりすぎて表示不良が起こりやすくなることがある。また肉厚が０．０５ｍｍ未満では、実用強度が不足したり、大板ガラスのたわみが大きくなったりして取り扱いが困難となることがある。好ましい肉厚は、０．１～０．５ｍｍである。 The thickness of the cover glass for a semiconductor package of the present invention is preferably 0.05 to 0.7 mm. As the wall thickness increases, it becomes an obstacle to weight reduction, and when it exceeds 0.7 mm, the distance from the solid-state imaging device becomes too close, and display defects may easily occur. On the other hand, if the thickness is less than 0.05 mm, the practical strength may be insufficient, or the deflection of the large plate glass may increase, making handling difficult. A preferable thickness is 0.1 to 0.5 mm.
　次に本発明の半導体パッケージ用カバーガラスの製造方法を説明する。 Next, a method for manufacturing a semiconductor package cover glass of the present invention will be described.
　まず所望の組成及び特性を有するガラスとなるようにガラス原料調合物を準備する。目標とするガラス組成及び特性は既述の通りであり、ここでは説明を割愛する。ガラス原料は、Ｕ、Ｔｈ等の不純物が少ない高純度原料を使用する。より具体的には、Ｕの含有量が１００ｐｐｂ以下（好ましくは２０ｐｐｂ以下）、Ｔｈの含有量が２００ｐｐｂ以下（好ましくは４０ｐｐｂ以下）となるように高純度原料を選択する。 First, a glass raw material formulation is prepared so as to obtain a glass having a desired composition and characteristics. The target glass composition and characteristics are as described above, and will not be described here. As the glass raw material, a high-purity raw material with few impurities such as U and Th is used. More specifically, the high-purity raw material is selected so that the U content is 100 ppb or less (preferably 20 ppb or less) and the Th content is 200 ppb or less (preferably 40 ppb or less).
　次いで調合したガラス原料を溶融槽に投入して溶融する。溶融槽は、白金容器を使用しても良いが、ガラス中に白金ブツが混入しやすいため、できれば使用しない方がよい。耐火物製の溶融槽を使用する場合、少なくとも溶融槽の内壁（天井、側面、底面）は、Ｕ、Ｔｈの少ない耐火物から作製することが好ましい。具体的には、アルミナ耐火物（例えばアルミナ質電鋳レンガ）や石英耐火物（例えばシリカブロック）が侵食しにくく、しかもＵ、Ｔｈの含有量が各々１ｐｐｍ以下であり、Ｕ、Ｔｈのガラスへの溶出が少ないため好ましい。 Next, the prepared glass material is put into a melting tank and melted. Although a platinum container may be used for the melting tank, it is better not to use it if possible because platinum particles are easily mixed in the glass. In the case of using a refractory melting tank, it is preferable that at least the inner walls (ceiling, side surfaces, and bottom surface) of the melting tank are made of refractories with less U and Th. Specifically, alumina refractories (for example, alumina-based electrocast bricks) and quartz refractories (for example, silica blocks) are less likely to erode, and U and Th contents are each 1 ppm or less. This is preferable because of less elution.
　次いで溶融ガラスの均質化（脱泡・脈理除去）を清澄槽で行う。この清澄槽は、耐火物や白金から作製すれば良い。尚、ジルコニア耐火物は、放射性同位元素を多く含むため、清澄槽の内壁材料に使用することは避けるべきである。 Next, homogenization (defoaming and striae removal) of the molten glass is performed in a clarification tank. What is necessary is just to produce this clarification tank from a refractory material or platinum. Zirconia refractories contain a lot of radioisotopes and should not be used for the inner wall material of clarification tanks.
　その後、均質化された溶融ガラスをオーバーフローダウンドロー法で板状に成形し、所望の厚みを有する板ガラスを得る。 Thereafter, the homogenized molten glass is formed into a plate shape by the overflow down draw method to obtain a plate glass having a desired thickness.
　こうして得られた板ガラスを所定の寸法に細断加工し、必要に応じて面取り加工することによってカバーガラスを作製する。 The cover glass is produced by chopping the plate glass thus obtained into a predetermined size and chamfering as necessary.
　このようにして得られるパッケージ用カバーガラスは、上記の基本組成を有しつつ、高純度原料と、不純物が混入し難いように整備された溶融環境を採用している。それゆえ、所望の特性を得ることができ、しかもＵ、Ｔｈ、Ｆｅ２Ｏ３、ＰｂＯ、ＴｉＯ２、ＺｒＯ２等の含有量を精密に制御することが可能である。 The package cover glass thus obtained employs a high-purity raw material and a molten environment prepared so that impurities are hardly mixed while having the above basic composition. Therefore, desired characteristics can be obtained, and the contents of U, Th, Fe 2 O 3 , PbO, TiO 2 , ZrO 2 and the like can be precisely controlled.
　以下、実施例に基づいて本発明のパッケージ用カバーガラスを説明する。 Hereinafter, the cover glass for a package of the present invention will be described based on examples.
　表１、２は、本発明のパッケージ用カバーガラスの実施例（試料Ｎｏ．１～１１）を示すものである。 Tables 1 and 2 show examples (sample Nos. 1 to 11) of the cover glass for a package of the present invention.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　まず表の組成となるように調製した高純度ガラス原料を、白金ロジウム、アルミナ、石英のいずれかから作製されたルツボに投入し、攪拌機能を有する電気溶融炉中で１５５０℃、６時間の条件で溶融し、その溶融ガラスをカーボン板上に流し出した。さらに、この板ガラスを徐冷してガラス試料とし、各種の評価に供した。 First, a high-purity glass raw material prepared so as to have the composition shown in the table is put into a crucible made from any of platinum rhodium, alumina, and quartz, and the conditions of 1550 ° C. and 6 hours in an electric melting furnace having a stirring function The molten glass was poured out onto a carbon plate. Furthermore, this plate glass was gradually cooled to obtain a glass sample, which was subjected to various evaluations.
　表から明らかなように、各ガラス試料は、密度、熱膨張係数、α線放出量について、半導体パッケージ用カバーガラスに要求される条件を満足するものであった。また１０２．５ｄＰａ・ｓの粘度に相当する温度が１５２０℃以下であるため溶融性に優れており、液相温度が１０２５℃以下、液相粘度が１０５．０ｄＰａ・ｓ以上であるため、耐失透性に優れ、オーバーフローダウンドロー法で成形可能であることが確認された。 As is apparent from the table, each glass sample satisfied the conditions required for the cover glass for semiconductor packages in terms of density, thermal expansion coefficient, and α-ray emission amount. Moreover, since the temperature corresponding to the viscosity of 10 2.5 dPa · s is 1520 ° C. or lower, the meltability is excellent, the liquidus temperature is 1025 ° C. or lower, and the liquid phase viscosity is 10 5.0 dPa · s or higher. Therefore, it was confirmed that it was excellent in devitrification resistance and could be molded by the overflow down draw method.
　Ｕ、Ｔｈの含有量は、ＩＣＰ－ＭＡＳＳにより測定した。密度は、周知のアルキメデス法によって測定した。熱膨張係数は、ディラトメーターを用いて、３０～３８０℃の温度範囲における平均熱膨張係数を測定した。ヤング率は共振法によって測定した。比ヤング率は、曲げ共振法によって測定したヤング率と密度から算出した。液相温度は、各ガラス試料を３００～５００μｍの粒径に破砕し、これを白金ボートに入れ、温度勾配炉中に８時間保持してから、顕微鏡観察により、ガラス試料内部に失透（結晶異物）の見られた最高温度を測定し、その温度を液相温度とした。また液相温度におけるガラスの粘度を液相粘度とした。また歪点、及び徐冷点は、ＡＳＴＭ　Ｃ３３６－７１の方法に準じて測定し、軟化点は、ＡＳＴＭ　Ｃ３３８－９３の方法に準じて測定した。１０４ｄＰａ・ｓ温度、１０３ｄＰａ・ｓ温度、及び１０２．５ｄＰａ・ｓ温度は、周知の白金球引き上げ法によって求めた。１０２．５ｄＰａ・ｓ温度は、高温粘度である１０２．５ｄＰａ・ｓに相当する温度を測定したものであり、この値が低いほど溶融性に優れていることになる。α線放出量は、超低レベルα線測定装置（住友化学社製ＬＡＣＳ－４０００Ｍ）を用いて測定した。
　耐酸性は８０℃の１０％濃度塩酸に２４時間ガラス試料を浸漬し、試験前後に変化した試料の単位面積当たりの重量とした。 The contents of U and Th were measured by ICP-MASS. The density was measured by the well-known Archimedes method. As the thermal expansion coefficient, an average thermal expansion coefficient in a temperature range of 30 to 380 ° C. was measured using a dilatometer. Young's modulus was measured by the resonance method. The specific Young's modulus was calculated from the Young's modulus and density measured by the bending resonance method. The liquidus temperature is obtained by crushing each glass sample to a particle size of 300 to 500 μm, placing it in a platinum boat, holding it in a temperature gradient furnace for 8 hours, and then devitrifying (crystallizing) inside the glass sample by microscopic observation. The maximum temperature at which foreign matter) was observed was measured, and that temperature was defined as the liquidus temperature. The viscosity of the glass at the liquidus temperature was defined as the liquidus viscosity. The strain point and annealing point were measured according to the method of ASTM C336-71, and the softening point was measured according to the method of ASTM C338-93. The 10 4 dPa · s temperature, the 10 3 dPa · s temperature, and the 10 2.5 dPa · s temperature were determined by a well-known platinum ball pulling method. The 10 2.5 dPa · s temperature is obtained by measuring a temperature corresponding to a high temperature viscosity of 10 2.5 dPa · s, and the lower this value, the better the meltability. The amount of α-ray emission was measured using an ultra-low level α-ray measuring device (LACS-4000M manufactured by Sumitomo Chemical Co., Ltd.).
The acid resistance was defined as the weight per unit area of the sample changed before and after the test by immersing the glass sample in 10% hydrochloric acid at 80 ° C. for 24 hours.
　次に表１～２のＮｏ．１、２、３、６及び９のガラスについて、試験溶融槽（アルミナ耐火物製）で溶融し、オーバーフローダウンドロー法で厚み０．５ｍｍの板状に成形した。次いでガラス表面を研磨することなく、さらにレーザースクライブによって細断加工を施すことによって、縦寸法１４ｍｍ、横寸法１６ｍｍのカバーガラスを作製した（試料Ａ～Ｅ）。こうして得られたカバーガラスの表裏の透光面（第１透光面と第２透光面）の表面粗さ（Ｒａ）を、触針式表面粗さ測定機タリステップ（Ｔａｙｌｅｒ－Ｈｏｂｓｏｎ社製）を用いて測定した。その結果を表３に示す。 Next, No. in Tables 1-2. Glasses 1, 2, 3, 6 and 9 were melted in a test melting tank (made of alumina refractory) and formed into a plate shape having a thickness of 0.5 mm by an overflow down draw method. Next, a cover glass having a longitudinal dimension of 14 mm and a transverse dimension of 16 mm was produced by subjecting the glass surface to further chopping by laser scribing (Samples A to E). The surface roughness (Ra) of the front and back translucent surfaces (the first translucent surface and the second translucent surface) of the cover glass obtained in this way was measured using a stylus type surface roughness measuring instrument Taly Step (Tayler-Hobson). ). The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３から明らかなように、実施例のカバーガラスは、いずれも第１透光面と第２透光面の表面粗さ（Ｒａ）が０．２３ｎｍ以下であり、極めて良好な平滑面を有していた。 As is apparent from Table 3, the cover glass of each example has a surface roughness (Ra) of the first light-transmitting surface and the second light-transmitting surface of 0.23 nm or less, and has a very good smooth surface. Was.
　本発明のパッケージ用カバーガラスは、固体撮像素子パッケージ用カバーガラスとして好適であり、これ以外にも、レーザーダイオードを収納するパッケージを始めとして、各種半導体パッケージのカバーガラスとして使用することができる。また、このカバーガラスは、３０～３８０℃の温度範囲における平均熱膨張係数が９０～１８０×１０－７／℃であるため、プラスチックパッケージ以外にも、樹脂、コバール合金、モリブデン合金、４２Ｎｉ－Ｆｅ合金、４５Ｎｉ－Ｆｅ合金等で作製された各種パッケージに適用することが可能である。
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１０年９月９日出願の日本特許出願（特願２０１０－２０１６３０）に基づくものであり、その内容はここに参照として取り込まれる。 The cover glass for a package of the present invention is suitable as a cover glass for a solid-state imaging device package, and besides this, it can be used as a cover glass for various semiconductor packages including a package containing a laser diode. Further, since this cover glass has an average coefficient of thermal expansion of 90 to 180 × 10 −7 / ° C. in the temperature range of 30 to 380 ° C., in addition to the plastic package, resin, Kovar alloy, molybdenum alloy, 42Ni—Fe The present invention can be applied to various packages made of an alloy, 45Ni—Fe alloy or the like.
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on September 9, 2010 (Japanese Patent Application No. 2010-201630), the contents of which are incorporated herein by reference.

Claims (12)

  1. 　質量％で、ＳｉＯ２　５８～７５％、Ａｌ２Ｏ３　１．１～２０％、Ｂ２Ｏ３　０～１０％、Ｎａ２Ｏ　０．１～２０％、Ｋ２Ｏ　０～１１％、アルカリ土類金属酸化物　０～２０％含有し、３０～３８０℃の温度範囲における平均熱膨張係数が９０～１８０×１０－７／℃、ヤング率が６８ＧＰa以上、ガラスからのα線放出量が、０．０５ｃ／ｃｍ２・ｈｒ以下であることを特徴とする半導体パッケージ用カバーガラス。 By mass%, SiO 2 58-75%, Al 2 O 3 1.1-20%, B 2 O 3 0-10%, Na 2 O 0.1-20%, K 2 O 0-11%, alkali Contains 0 to 20% of earth metal oxide, has an average coefficient of thermal expansion of 90 to 180 × 10 −7 / ° C. in a temperature range of 30 to 380 ° C., Young's modulus of 68 GPa or more, and emits α rays from glass. A cover glass for a semiconductor package, characterized by being 0.05 c / cm 2 · hr or less.
  2. 　ガラス中のＵ含有量が１００ｐｐｂ以下、Ｔｈ含有量が２００ｐｐｂ以下であることを特徴とする請求項１に記載の半導体パッケージ用カバーガラス。 2. The cover glass for a semiconductor package according to claim 1, wherein the U content in the glass is 100 ppb or less and the Th content is 200 ppb or less.
  3. 　ＺｒＯ２、Ａｓ２Ｏ３及びＢａＯを実質的に含有しないことを特徴とする請求項１又は２に記載の半導体パッケージ用カバーガラス。 3. The cover glass for a semiconductor package according to claim 1, wherein ZrO 2 , As 2 O 3 and BaO are not substantially contained.
  4. 　アルカリ金属酸化物およびアルカリ土類金属酸化物の合量が２１～３５質量％であることを特徴とする請求項１～３の何れかに記載の半導体パッケージ用カバーガラス。 4. The cover glass for a semiconductor package according to claim 1, wherein the total amount of the alkali metal oxide and the alkaline earth metal oxide is 21 to 35% by mass.
  5. 　液相温度におけるガラス粘度が１０４．７ｄＰａ・ｓ以上であることを特徴とする請求項１～４の何れかに記載の半導体パッケージ用カバーガラス。 5. The cover glass for a semiconductor package according to claim 1, wherein the glass viscosity at the liquidus temperature is 10 4.7 dPa · s or more.
  6. 　未研磨の表面を有することを特徴とする請求項１～５の何れかに記載の半導体パッケージ用カバーガラス 6. The cover glass for a semiconductor package according to claim 1, which has an unpolished surface.
  7. 　質量基準で、ＳｉＯ２／（Ａｌ２Ｏ３＋Ｋ２Ｏ）の比が１～１２であることを特徴とする請求項１～６の何れかに記載の半導体パッケージ用カバーガラス。 7. The cover glass for a semiconductor package according to claim 1, wherein a ratio of SiO 2 / (Al 2 O 3 + K 2 O) is 1 to 12 on a mass basis.
  8. 　質量基準で、（Ｎａ２Ｏ＋Ｋ２Ｏ）／Ｎａ２Ｏの比が１．１～１０であることを特徴とする請求項１～７の何れかに記載の半導体パッケージ用カバーガラス。 8. The cover glass for a semiconductor package according to claim 1, wherein a ratio of (Na 2 O + K 2 O) / Na 2 O is 1.1 to 10 on a mass basis.
  9. 　ＣＭＯＳ用プラスチックパッケージに使用されることを特徴とする請求項１～８の何れかに記載の半導体パッケージ用カバーガラス。 9. The cover glass for a semiconductor package according to claim 1, which is used for a plastic package for CMOS.
  10. 　質量％で、ＳｉＯ２　５８～７５％、Ａｌ２Ｏ３　１．１～２０％、Ｂ２Ｏ３　０～１０％、Ｎａ２Ｏ　０．１～２０％、Ｋ２Ｏ　０～１１％、アルカリ土類金属酸化物　０～２０％含有し、３０～３８０℃の温度範囲における平均熱膨張係数が９０～１８０×１０－７／℃、ヤング率が６８ＧＰa以上となるようにガラス原料を調製し、溶融した後、オーバーフローダウンドロー法を用いて板状に成形するとともに、ガラスからのα線放出量が０．０５ｃ／ｃｍ２・ｈｒ以下となるようにガラス原料及び溶融設備の選択を行うことを特徴とする半導体パッケージ用カバーガラスの製造方法。 By mass%, SiO 2 58-75%, Al 2 O 3 1.1-20%, B 2 O 3 0-10%, Na 2 O 0.1-20%, K 2 O 0-11%, alkali A glass raw material is prepared so that it contains 0 to 20% of an earth metal oxide, has an average coefficient of thermal expansion of 90 to 180 × 10 −7 / ° C. in a temperature range of 30 to 380 ° C., and a Young's modulus of 68 GPa or more. After melting, forming into a plate shape using the overflow downdraw method, and selecting the glass raw material and the melting equipment so that the α ray emission from the glass is 0.05 c / cm 2 · hr or less. A method for producing a semiconductor package cover glass.
  11. 　ガラス中のＵ含有量が１００ｐｐｂ以下、Ｔｈ含有量が２００ｐｐｂ以下となるように、原料バッチの選択及び溶融条件の調節を行うことを特徴とする請求項１０に記載の半導体パッケージ用カバーガラスの製造方法。 The manufacturing of the cover glass for a semiconductor package according to claim 10, wherein the raw material batch is selected and the melting conditions are adjusted so that the U content in the glass is 100 ppb or less and the Th content is 200 ppb or less. Method.
  12. 　ＺｒＯ２、Ａｓ２Ｏ３及びＢａＯを実質的に含有しないバッチを使用することを特徴とする請求項１０又は１１に記載の半導体パッケージ用カバーガラスの製造方法。 ZrO 2, As 2 O 3 and substantially claim 10 or 11 the method of manufacturing a semiconductor package cover glass according to, characterized by using a free batch BaO.
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